US3351648A - Process for preparing iron tetracarbonyl compounds with mono-olefinic ligands - Google Patents

Process for preparing iron tetracarbonyl compounds with mono-olefinic ligands Download PDF

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US3351648A
US3351648A US327825A US32782563A US3351648A US 3351648 A US3351648 A US 3351648A US 327825 A US327825 A US 327825A US 32782563 A US32782563 A US 32782563A US 3351648 A US3351648 A US 3351648A
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iron tetracarbonyl
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Erwin L Weiss
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    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds

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  • This invention relates to novel olefinic iron tetracarbonyl compounds or complexes and a process for their preparation. More particularly, the present invention relates to novel ar-olefinic iron tetracarbonyl complexes and a novel process for their preparation.
  • 1r-olefin iron tetracarbonyl complexes of the formula are provided where L is an olefinic ligand characterized by at least one carbonyl group, alpha to an unsaturated carbon to carbon bond.
  • olefinic ligands contemplated for use in this invention may be described as substituted ethylenes with carbonyl-containing substituents in the alpha position to an unsaturated carbon to carbon bond. These ligands may be further characterized as dunsaturated carbonyl compounds which are capable of forming the novel iron tetracarbonyl complexes in accordance with the process aspects of 'this invention.
  • such ligands may be a,t3-unsaturated monoand dicarboxylic acids, anhydrides, esters, amides and aldehydes, and illustratively include acrylic acid, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic'acid amide, acrolein, maleic acid, maleic ,acid methyl ester, maleic acid dimethyl ester, maleic acid anhydride, citraconic acid, citraconic acid anhydride, cinnarnic acid, cinnamic acid methyl ester, and cinnamic aldehyde.
  • the unsaturated carbon to carbon bond or group is activated by an adjacent carbonyl group and thus reacts readily with the di-iron enneacarbonyl to form the novel complexes of this invention in good yield.
  • This is particularly surprising in view of the fact-that di-iron enneacarbonyl is generally believed to be less active than iron pentacarbonyl or tri-iron dodecacarbonyl.
  • the process of this invention whereby unusually high yields of the novel iron tetracarbonyl complexes are obtained, is carried out by reacting the di-iron enneacarbonyl with the olefinic ligand at a temperature of from to about 100 C., usually at a temperature of from 0 to 80, C. and. preferably at a temperature of from 30 to 60 C. at atmospheric pressure. Uniformly good results have been obtained at temperatures of about 40 to about 45 C.
  • the reaction is normally carried out in aromatic or aliphatic inert solvents, as for example cyclohexane, benzene, xylene, ketones such as acetone, petroleum ether and the like. Normally, the reaction will be carried out at atmospheric pressures, although subatmospheric or superatmospheric conditions may be employed.
  • the reaction time is that which is sufiicient to form the complex, but typically runs from an hour up to four hours or more.
  • the compounds of this invention may be useful as fuel additives and in metal plating in view of the fact that they contain metal in the zero va'lent state and may be characterized as being volatile. They are capable of creating free radicals, either by thermal decomposition or reaction with other reagents, and therefore may be employed as polymerization initiators. They may be modified by the reaction of their functional groups, as for example --CHO, -COOH, OOR, CONH and the like, and thus are useful as chemical intermediates. Thus, for example, the esterification of these compounds with acrylic, maleic, fumaric or other ligands is contemplated. In addition, they may be polycondensed with polyhydric alcohols such as diols to produce metal-containing polymers having new and desirable properties.
  • Example 1 Equimolecular quantities of maleic acid anhydride (0.05 mole,'4.90 grams, freshly'sublin'ied) and di-iron enneacarbonyl (18.20 grams) were suspended in 50 ml. of absolute benzene and stirred for 4 hours at 45 C. A yellow precipitate of the complex compound was formed in an amount corresponding to the decomposition of the iron carbonyl; the precipitate was filtered, washed with benzene and dried in a vacuum to yield 11.16 grams of product. i
  • Examples 2-18 The complexes identified below and further in Table I hereinafter were prepared in a manner substantially similar to that described in Example 1 above, at a temperature of40to 45 c.
  • Example 3 Maleinimide iron tetracarbonyl after a reaction of 2 hours in benzene.
  • Example4 Maleic acid iron tetracarbonyl after a reaction time of 1 hour in 50 ml. of acetone.
  • Example 8 Fumaric acid iron tetracarbonyl after 2 hours in 50 ml. of acetone.
  • Example 9 Fumaric acid dimethyl ester iron tetracarbonyl after a 1-hour reaction in benzene.
  • Example 15 Citraconic acid anhydride iron tetracarbonyl obtained as a crude product in the form of a brown oil after a 4- hour reaction.
  • Example- Maleic acid methyl ester iron tetracarbonyl obtained as a crystalline mass after a 2-hour reaction period.
  • Example 6 Maleic acid di-rnet-hyl ester iron tetracarbonyl obtained after a reaction of 1.5 hours as an oil.
  • Example 12 1O Acrylic acid ethyl ester iron tetracarbonyl obtained after a reaction period of 2 hours as an oil.
  • Example 14 Acrolein iron tetracarbonyl reacted at 35 C. for a pc- 15 riod of 3 hours obtained as an oil.
  • Example 16 Cinnamic acid methyl ester iron tetracarbonyl obtained after a reaction of 1 hour as an oil.
  • Example 18 Methacrylic acid iron tetracarbonyl obtained after a l-hour reaction as an oil which solidified at 0 C.
  • Example 9 The compound of Example 9 from acetone with a few drops of semi-concentrated hydrogen chloride.
  • the compound of Example 5 from benzene.
  • the compound of Examples 7 and 15 from acetone.
  • the compound of Example 16 from petroleum ether.
  • the compound of Example 17 from a 1:1 benzenepetroleum ether mixture.
  • the compounds of Examples 6, 10, 11, 13, 14 and 18 were purified by vacuum sublimation.
  • L is a mono-olefinic ligand characterized by at least one carbonyl group alpha to the unsaturated carbon to carbon bond which comprises reacting the said monoolefinic ligand with di-iron enneacarbonyl at a temperature of from about to about 60 C. at atmospheric pressure.
  • a process for preparing 1r-olefin iron tetracarbonyl compounds of the formula 1r-LF(CO) where L is a mono-olefinic ligand characterized by at least one carbonyl group alpha to the unsaturated carbon to carbon bond which comprises reacting in an inert solvent the said mono-olefinic ligand with di-iron enneacar-bonyl at a temperature of from about 30 to about 60 C. at atmospheric pressure.

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

United States Patent Ofiice 3,351,648 Patented Nov. 7, 1967 3 351,648 PROCESS FOR PREP ARING IRON TETRACAR- BONYL COMPOUNDS WlTH MONO-OLEFINIC LIGANDS Erwin L. Weiss, Grand-Laney, Geneva, Switzerland, assignor to American Cyanamid Company, Stamford,
Conn., a corporation of Maine No Drawing. Filed Dec. 3, 1963, Ser. No. 327,825 4 Claims. (Cl. 260-439) This invention relates to novel olefinic iron tetracarbonyl compounds or complexes and a process for their preparation. More particularly, the present invention relates to novel ar-olefinic iron tetracarbonyl complexes and a novel process for their preparation.
In accordance with the present invention, 1r-olefin iron tetracarbonyl complexes of the formula are provided where L is an olefinic ligand characterized by at least one carbonyl group, alpha to an unsaturated carbon to carbon bond.
The olefinic ligands contemplated for use in this invention may be described as substituted ethylenes with carbonyl-containing substituents in the alpha position to an unsaturated carbon to carbon bond. These ligands may be further characterized as dunsaturated carbonyl compounds which are capable of forming the novel iron tetracarbonyl complexes in accordance with the process aspects of 'this invention. Illustratively, such ligands may be a,t3-unsaturated monoand dicarboxylic acids, anhydrides, esters, amides and aldehydes, and illustratively include acrylic acid, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic'acid amide, acrolein, maleic acid, maleic ,acid methyl ester, maleic acid dimethyl ester, maleic acid anhydride, citraconic acid, citraconic acid anhydride, cinnarnic acid, cinnamic acid methyl ester, and cinnamic aldehyde.
In accordance with this invention, these and their equivalent olefinic ligands are reacted with di-iron enneacarbonyl [Fe (CO) in accordance with the equation:
to produce the novel iron tetracarbonyl monoolefinic complexes of this invention.
Thus, I have discovered in accordance with this invention that the presence of a carbonyl group in the alpha -position-totin-unsaturated carbon to carbon bond of a substituted ethylene causes such ligands to react with diiron enneacarbonyl to form iron tetracarbonyl complexes in surprisingly high yields, as for example up to 93%.
It is an important and surprising discovery of the present invention that the unsaturated carbon to carbon bond or group is activated by an adjacent carbonyl group and thus reacts readily with the di-iron enneacarbonyl to form the novel complexes of this invention in good yield. This is particularly surprising in view of the fact-that di-iron enneacarbonyl is generally believed to be less active than iron pentacarbonyl or tri-iron dodecacarbonyl.
It is presently known that acrylonitrile may be employed to form acrylonitrile iron tetracarbonyl complexes. Thus, this complex has been produced in very poor yield (on the order of 2 to 3%) by reacting acrylonitrile and various iron carbonyls.
The process of this invention, whereby unusually high yields of the novel iron tetracarbonyl complexes are obtained, is carried out by reacting the di-iron enneacarbonyl with the olefinic ligand at a temperature of from to about 100 C., usually at a temperature of from 0 to 80, C. and. preferably at a temperature of from 30 to 60 C. at atmospheric pressure. Uniformly good results have been obtained at temperatures of about 40 to about 45 C.
The reaction is normally carried out in aromatic or aliphatic inert solvents, as for example cyclohexane, benzene, xylene, ketones such as acetone, petroleum ether and the like. Normally, the reaction will be carried out at atmospheric pressures, although subatmospheric or superatmospheric conditions may be employed.
The reaction time is that which is sufiicient to form the complex, but typically runs from an hour up to four hours or more.
The compounds of this invention, like many organometallic compounds, may be useful as fuel additives and in metal plating in view of the fact that they contain metal in the zero va'lent state and may be characterized as being volatile. They are capable of creating free radicals, either by thermal decomposition or reaction with other reagents, and therefore may be employed as polymerization initiators. They may be modified by the reaction of their functional groups, as for example --CHO, -COOH, OOR, CONH and the like, and thus are useful as chemical intermediates. Thus, for example, the esterification of these compounds with acrylic, maleic, fumaric or other ligands is contemplated. In addition, they may be polycondensed with polyhydric alcohols such as diols to produce metal-containing polymers having new and desirable properties.
In order to illustrate the present invention, the following examples are given primarily by way of illustration. No specific details or enumerations contained therein should be construed as limitations except insofar as they appear in the appended claims. All parts and percentages are by weight unless otherwise specifically designated. v
In carrying out the examples referred to hereinbelow, air and bright daylight were excluded during the purification of the compound. All solvents were carefully made absolute. The melting points were determined in a heating stage microscope and are uncorrected.
All of the substituted ethylenes with substituents containing carbonyl groups in the alpha position to the carbon to carbon unsaturated double bond were purchased commercially and purified where needed, with the exception of ma'leinimide, maleic acid methyl ester, citraconic acid and fumaric acid dimethyl ester, which were prepared in accordance withlliteratureprocedures.
Example 1 Equimolecular quantities of maleic acid anhydride (0.05 mole,'4.90 grams, freshly'sublin'ied) and di-iron enneacarbonyl (18.20 grams) were suspended in 50 ml. of absolute benzene and stirred for 4 hours at 45 C. A yellow precipitate of the complex compound was formed in an amount corresponding to the decomposition of the iron carbonyl; the precipitate was filtered, washed with benzene and dried in a vacuum to yield 11.16 grams of product. i
After drawing off the solvent and iron pentacarbonyl, an additional .73 gram was obtained from the yellow filtrate. Thecrude yield was 89% of the theoretical value and 3.00 grams of the crude product was dissolved in ml. of acetone.
After concentration and storage at 0 C., 2.34 grams of the analytically pure compound (70% of the theoretical yield) was crystallized out of the filtered solution.
Examples 2-18 The complexes identified below and further in Table I hereinafter were prepared in a manner substantially similar to that described in Example 1 above, at a temperature of40to 45 c.
In connection with these preparations, the following observations were made.
A The following products precipitated out directly because of their low solubility:
Example 3 Maleinimide iron tetracarbonyl after a reaction of 2 hours in benzene.
Example4 Maleic acid iron tetracarbonyl after a reaction time of 1 hour in 50 ml. of acetone.
Example 7 Citraconic acid iron tetracarbonyl after 3 hours in benzene.
Example 8 Fumaric acid iron tetracarbonyl after 2 hours in 50 ml. of acetone.
Example 9 Fumaric acid dimethyl ester iron tetracarbonyl after a 1-hour reaction in benzene.
Example 13 Acrylamide iron tetracarbonyl after 2 hours in benzene.
Example 15 Example 2 Citraconic acid anhydride iron tetracarbonyl obtained as a crude product in the form of a brown oil after a 4- hour reaction.
Example- Maleic acid methyl ester iron tetracarbonyl obtained as a crystalline mass after a 2-hour reaction period.
Example 6 Maleic acid di-rnet-hyl ester iron tetracarbonyl obtained after a reaction of 1.5 hours as an oil.
TABLE L-IRON TETRAOARBONYL COMPLEX 4 Example 10 5 Example 11 Acrylic acid methyl ester iron tetracarbonyl obtained after a reaction of 2 hours as a semi-solid.
Example 12 1O Acrylic acid ethyl ester iron tetracarbonyl obtained after a reaction period of 2 hours as an oil.
Example 14 Acrolein iron tetracarbonyl reacted at 35 C. for a pc- 15 riod of 3 hours obtained as an oil.
Example 16 Cinnamic acid methyl ester iron tetracarbonyl obtained after a reaction of 1 hour as an oil. a i
20 Example 1 7 Cinnamic aldehyde iron tetracarbonyl obtained after a reaction of 1 hour as an oil.
Example 18 Methacrylic acid iron tetracarbonyl obtained after a l-hour reaction as an oil which solidified at 0 C.
CFurther purification was carried out on the complexes identified above and in Table I below by recrystallization from the following solvents: The compound of Examples 3, 4 and 8 from a methylene chloride-petroleum ether solvent.
The compound of Example 9 from acetone with a few drops of semi-concentrated hydrogen chloride. The compound of Example 5 from benzene. The compound of Examples 7 and 15 from acetone. The compound of Example 16 from petroleum ether. The compound of Example 17 from a 1:1 benzenepetroleum ether mixture. The compounds of Examples 6, 10, 11, 13, 14 and 18 were purified by vacuum sublimation.
The compound of Example 12 by vacuum distillation under the conditions specifically set forth in Table I.
The results of the above examples are tabulated in Table I hereinbelow.
ES WITH :1, B-UNSATURAIED CARBONYL LIGANDS Yield Example Ligand Compound (Pure Properties Melting Point, C;
No. Product),
Percent /CCH 1 Maleic acid anhydride 0 Fe(C 0)., Pale yellow needles About 148 (with decomposition) Brown color from about C-CH /CCH 2 Citraconlc acldanhydride-.. O\ Fe(C O)4 60 Yellow crystals 92-93 (with decomposition).
A CC CH3 /CCH 3 Maleinimide HN\ Fe(CO)4 77 d0 1. Decomposition from about 159.
C-OH O H O O C CH 4 Maleic acid Fe(C O)4 93 Yellow prisms Decomposition about HO O C CH Brown color from ab rut 130.
TABLE I- Continud Yield Example Ligand Compound (Pure Properties Melting Point, C.
No. Product),
Percent CHaO O C C H 5 Maleic acid methyl cster Fc(CO)4 70 Yellow prisms .1 About 93 (with decomposition).
H O O C C H C H3 0 0 C CH 6 Maleic acid dimethy ester I] s Fe(CO) 68 Yellow needles. Sublunes at 36-37".
CHaO O C CH 35710- Torr.
H O O C CH 7 Citraconic acid {1 Fe(CO) 80 Yellow crystals Decomposition from about 90.
11 O O C C CH3 H O O C CH 8 Fumanc acid Fe(CO) 79 Pale yellow crystals Decomposition from about 155.
11 C C O O H 01130 O C CH 9. Furnaric acid dimethyl ester. ll Fe(CO) 86 Pale yellow fine needles About 137 (with decomposition).
HC C O 0 CH3 CH3 10. Acrylic acid [I Fe(CO)4 68 Yellow prisms. Sublimes from 104-106" (with decomposition).
HO 0 O OH about 80-90"/10- Torr.
C H: 11 Acrylic acid methyl ester Fe(CO)4 71 Large pale yellow crystals. 28-285".
110 C 0 0 CH Sublimes from 710- Torr.
. C H: 12 Acrylic acid ethyl ester. I] Fe(CO)4 64 Yellow liquid Sdp. 6065/l About -2.
HO C O 0 0 11 Torr.
C H: 13. Acrylic amide Fe(CO)4 68 Yellow prisms. Sublimes from nil-117 (with decomposition).
HC 0 ONHi about 80-95710- Torr.
CH; 14 Acrolein- Fe(CO)4 50 Yellow crystals. Sublirnes 34-35.? Transformation at 31.
HC CHO 20"/10- Torr.
O 0H5C H 15 Cinnamic acid Fe(CO)4 80 Yellow crystals Decomposition from about 110.
HO O O 011 C 0115011 16 Cinnamic acid methyl ester II Fe(C0)4 64 do 63.5".
HC C 0 0 CH3 C 011 0 H 17- Cinnamie aldehyde H Fe(CO)4 36 do 87-92.
HC CH0 CH: 18 Methacrylic acid Fe(CO)4 15 .-d0- 70-73".
' CHaC C O 011 where L is a mono-olefinic ligand characterized by at least one carbonyl group alpha to the unsaturated carbon to carbon bond which comprises reacting the said monoolefinic ligand with di-iron enneacarbonyl at a temperature of from about to about 60 C. at atmospheric pressure.
2. A process for preparing 1r-olefin iron tetracarbonyl compounds of the formula 1r-LF(CO) where L is a mono-olefinic ligand characterized by at least one carbonyl group alpha to the unsaturated carbon to carbon bond which comprises reacting in an inert solvent the said mono-olefinic ligand with di-iron enneacar-bonyl at a temperature of from about 30 to about 60 C. at atmospheric pressure.
3. A process according to claim 2 in which the monoolefinic ligand is maleic anhydride.
4. A process according to claim 2 in which the monoolefinic ligand is maleinimide.
References Cited UNITED STATES PATENTS 3,126,401 3/1964 Ecke 260-439 OTHER REFERENCES I. Chatt. et al. in H. Zeiss Organo-metallic Chemistry, ACS Monograph Series No. 147, p. 482, Rheinhold Pub. Corp, New York, 1960.
Schenck et al., Tetrahedron Letters, N0. 23, pp. 1059- 1064, November 1962.
TOBIAS E. LEVOW, Primary Examiner.
E. C. BARTLETT, A. P. DEMERS, Assistant Examiners.

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1. A PROCESS FOR PREPARING $-OLEFINE IRON TETRACARBONYL COMPOUNDS OF THE FORMULA
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3414600A (en) * 1965-08-16 1968-12-03 Rhone Poulenc Sa Organotricarbonyl ferrates and the preparation thereof
EP2246112A1 (en) * 2007-11-23 2010-11-03 China Fuel (Huaibei) Bioenergy Technology Development Co., Ltd System for bionic catalytic hydrolyzing cellulose and its use in producing liquid fuel from cellulose biomass
US20140296468A1 (en) * 2011-12-01 2014-10-02 Dow Corning Corporation Hydrosilylation Reaction Catalysts and Curable Compositions and Methods for Their Preparation and Use

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3126401A (en) * 1964-03-24 Iron tricarbonyl complexes of

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3126401A (en) * 1964-03-24 Iron tricarbonyl complexes of

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3414600A (en) * 1965-08-16 1968-12-03 Rhone Poulenc Sa Organotricarbonyl ferrates and the preparation thereof
EP2246112A1 (en) * 2007-11-23 2010-11-03 China Fuel (Huaibei) Bioenergy Technology Development Co., Ltd System for bionic catalytic hydrolyzing cellulose and its use in producing liquid fuel from cellulose biomass
EP2246112A4 (en) * 2007-11-23 2010-12-15 China Fuel Huaibei Bioenergy T System for bionic catalytic hydrolyzing cellulose and its use in producing liquid fuel from cellulose biomass
US20140296468A1 (en) * 2011-12-01 2014-10-02 Dow Corning Corporation Hydrosilylation Reaction Catalysts and Curable Compositions and Methods for Their Preparation and Use
US9073950B2 (en) * 2011-12-01 2015-07-07 Dow Corning Corporation Hydrosilylation reaction catalysts and curable compositions and methods for their preparation and use

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